Use of a first film and a second film to improve seal strength of a water-soluble unit dose article

ABSTRACT

The use of a first water-soluble film and a second water-soluble film to make a unit dose article and the use of the unit dose article.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation of U.S. patent application Ser. No. 15/620,344,filed Jun. 12, 2017 (U.S. Pat. No. 10,907,117), which claims benefitunder 35 U.S.C. § 119(e) of U.S. Provisional Patent Application No.62/349,639 filed Jun. 13, 2016, the disclosures thereof which are herebyincorporated by reference herein.

NAMES OF PARTIES TO A JOINT RESEARCH AGREEMENT

The claimed invention was made as a result of activities undertakenwithin the scope of a joint research agreement between MonoSol, LLC andProcter & Gamble Company.

FIELD

The present disclosure relates to the use of a first water-soluble filmand a second water-soluble film to make a unit dose article and the useof said unit dose article.

BACKGROUND

Water-soluble detergent unit dose articles are preferred by users (e.g.,consumers) as they are a convenient, efficient and clean way of dosingcompositions, e.g. detergent during a wash process. The water-solubleunit dose form means that the user does not need to measure the dosethemselves nor do they suffer from accidental spillage of thecomposition, which some users find messy and inconvenient.

However, such water-soluble unit dose articles can suffer from prematurerupture during storage, especially rupture due to failure of the sealbetween the two films making up with the unit dose article. Often suchunit dose articles are stored in flexible resealable bags or rigidcloseable tubs. In either case premature rupture of a water-soluble unitdose article can negatively affect the dosing experience as the internalcontents of the ruptured unit dose article contaminate the othernon-ruptured unit dose articles. Hence, the user may find the dosingexperience ‘messy’ and inconvenient.

Furthermore, seal failure can occur during the unit dose articlemanufacturing process.

Such failure results in wasted resource and time as the ruptured pouchesneed to be scrapped.

Therefore, there is a need in the art to improve the seal strength ofthe seal area of water-soluble unit dose articles to reduce prematurerupture of the unit dose articles ahead of use by the user and alsoduring manufacture.

There is also a need in the art to improve the user dosing experience.

It was surprisingly found that the use of a water-soluble unit dosearticle according to the present invention overcame these technicalproblems.

SUMMARY

A first aspect of the present disclosure is the use of a firstwater-soluble film and a second water-soluble film in the manufacture ofa water-soluble unit dose article, optionally comprising a compositioncontained within the unit dose article, wherein the first water-solublefilm and the second water-soluble film are sealed together along a sealarea, in order to improve the seal strength in the seal area; whereinthe first water-soluble film and the second water-soluble film arechemically different to one another, and wherein the first water-solublefilm has a first water capacity, and wherein the second water-solublefilm has a second water capacity, wherein the first water capacity isless than the second water capacity, and wherein the difference betweenthe water capacity of the first water soluble film and the secondwater-soluble film is between 0.01% and 1%.

A second aspect of the present disclosure is the use of a unit dosearticle comprising at least a first water-soluble film, a secondwater-soluble film and optionally a composition contained in the unitdose article, wherein the first water-soluble film, the secondwater-soluble film and the composition are according to the presentdisclosure herein, to improve the user dosing experience.

A third aspect of the disclosure is a process for dosing a unit dosearticle comprising the steps of;

obtaining a water-soluble unit dose article comprising at least a firstwater-soluble film, a second water-soluble film and a compositioncontained therein, wherein the first water-soluble film and the secondwater-soluble film are chemically different to one another, and whereinthe first water-soluble film has a first water capacity, and wherein thesecond water-soluble film has a second water capacity, wherein the firstwater capacity is less than the second water capacity and wherein thedifference between the water capacity of the first water soluble filmand the second water-soluble film is between 0.01% and 1%; and

contacting the water-soluble unit dose article with water to dissolve atleast a portion of a film thereof, thereby releasing the composition.

BRIEF DESCRIPTION OF THE DRAWINGS

The figures herein are illustrative in nature and are not intended to belimiting.

FIG. 1 shows a schematic illustration of the basic configuration of theunit dose article strength test and seal failure test.

FIG. 2 shows a side cross-sectional view of a pouch.

FIG. 3 shows a multi-compartment pouch.

DETAILED DESCRIPTION OF THE INVENTION

The Use

The present disclosure is directed to the use of a first water-solublefilm and a second water-soluble film in the manufacture of awater-soluble unit dose article, optionally comprising a compositioncontained within the unit dose article, wherein the first water-solublefilm and the second water-soluble film are sealed together along a sealarea, in order to improve the seal strength in the seal area. The unitdose article, the first water-soluble film, the second water-solublefilm and the optional composition are described in more detail below.

Preferably the use is to improve the seal strength in the seal area toreduce the volume of scrapped material during manufacture ofwater-soluble unit dose articles.

A further aspect of the present invention is the use of a unit dosearticle comprising at least a first water-soluble film, a secondwater-soluble film and optionally a composition contained within theunit dose article, wherein the first water-soluble film, the secondwater-soluble film and the optional composition are according to thepresent disclosure, to improve the user dosing experience.

Preferably, the user dosing experience comprises the user transferringor otherwise handling at least one water-soluble unit dose article, e.g.transferring it from a storage receptacle to another container orlocation for use. One or more of the water-soluble unit dose articlesmay be directly added to bulk water, e.g. for water-conditioningapplications, or dispersed on a substrate, e.g. land in the case ofagrochemical unit dose articles. The water-soluble unit dose article maybe handled by hand. The water-soluble unit dose article may be handledby a machine apparatus, e.g. a conveyor, sorter, or the like.

The user dosing experience for detergent unit dose article can comprisethe user transferring at least one water-soluble unit dose article froma storage receptacle to an automatic washing machine, preferably to thedrum of an automatic washing machine. Alternatively, the water-solubleunit dose article may be added to the drawer of an automatic washingmachine. A water-soluble unit dose detergent article may be added to thewashing machine by hand. A water-soluble unit dose detergent article maybe added to the drum by hand. Alternatively it may be dispensed from astorage receptacle into the washing machine, preferably the drum. Thoseskilled in the art will be aware of relevant storage receptacles.

Those skilled in the art will be aware of suitable automatic washingmachines. Those skilled in the art will also be aware that automaticwashing machines comprise a drum and a drawer and will be able to locatesaid drum or drawer and add both the fabrics and the water-soluble unitdose article thereto accordingly.

Those skilled in the art will be aware of relevant storage receptacles.Preferably, the storage receptacle is a flexible, preferably resealable,bag, a rigid, preferably recloseable, tub or a mixture thereof,preferably, wherein the storage receptacle comprises a child resistantclosure. Those skilled in the art will be aware of suitable childresistant closures.

Preferably, the improved user dosing experience comprises reduced messand increased convenience to the user during the dosing operation.Preferably, the improved user dosing experience comprises reducedinstances of premature rupture of the water-soluble unit dose articlesin handling machinery or the hand of the user, e.g. during transfer suchas whilst transferring them from a storage receptacle to a container foruse, e.g. a washing drum.

Without wishing to be bound by theory, it was surprisingly found thatthe use of two films have the characteristics of the present inventionimproved the seal strength of a water-soluble unit dose articlemanufactured from said films. By improving the seal strength, theinstances of premature rupture both during manufacture, storage andduring dosing by the user were all reduced.

A third aspect of the disclosure is a process for dosing a unit dosearticle comprising the steps of;

obtaining a water-soluble unit dose article comprising at least a firstwater-soluble film, a second water-soluble film and a compositioncontained therein, wherein the first water-soluble film and the secondwater-soluble film are chemically different to one another, and whereinthe first water-soluble film has a first water capacity, and wherein thesecond water-soluble film has a second water capacity, wherein the firstwater capacity is less than the second water capacity and wherein thedifference between the water capacity of the first water soluble filmand the second water-soluble film is between 0.01% and 1%; and

contacting the water-soluble unit dose article with water to dissolve atleast a portion of a film thereof, thereby releasing the composition.

The contacting may take between 5 minutes and 50 minutes, preferablybetween 5 minutes and 40 minutes, more preferably between 5 minutes and30 minutes, even more 20 preferably between 5 minutes and 20 minutes,most preferably between 6 minutes and 18 minutes.

The contacting may comprise the addition of between 10 L and 60 L,preferably between 10 L and 40 L, more preferably between 10 L and 30 L,most preferably between 10 L and 20 L of water to the unit dose article.

The temperature of the water may be between 10° C. and 45° C., orbetween 15° C. and 35° C.

Water-Soluble Unit Dose Article

The present invention is to the use of a first water-soluble film and asecond water-soluble film in the manufacture of a water-soluble unitdose article optionally comprising a composition contained within theunit dose article, wherein the first water-soluble film and the secondwater-soluble film are sealed together along a seal area, in order toimprove the seal strength in the seal area.

The water-soluble unit dose article comprises the first water-solublefilm and the second water-soluble film shaped such that the unit-dosearticle comprises at least one internal compartment surrounded by thewater-soluble films. The water-soluble films are sealed to one anothersuch to define the internal compartment and such that that the detergentor other composition does not leak out of the compartment duringstorage. However, upon contact with sufficient water, e.g. the additionof the water-soluble unit dose article to water, the water-soluble filmdissolves and releases the contents of the internal compartment into thewater (e.g., wash liquor).

The area in which the two films meet and are sealed together is referredto as the seal area. Often, the seal area comprises a ‘skirt’ or‘flange’ which comprises area of the first water-soluble film sealed toan area of the second water-soluble film and which generally protrudesout from the main body of the unit dose article. A preferred method ofmaking a unit dose article is described in more detail below.

The compartment should be understood as meaning a closed internal spacewithin the unit dose article, e.g. formed by the films, which holds thedetergent or other composition. During manufacture, the firstwater-soluble film according to the present invention may be shaped tocomprise an open compartment into which the detergent or othercomposition is added. The second water-soluble film according to thepresent invention is then laid over the first film in such anorientation as to close the opening of the compartment. The first andsecond films are then sealed together along a seal region.

The unit dose article may comprise more than one compartment, even atleast two compartments, or even at least three compartments. Thecompartments may be arranged in superposed orientation, i.e. onepositioned on top of the other. In such an orientation the unit dosearticle will comprise three films, top, middle and bottom. Preferably,the middle film will correspond to the second water-soluble filmaccording to the present invention and top and bottom films willcorrespond to the first water-soluble film according to the presentinvention. Alternatively, the compartments may be positioned in aside-by-side orientation, i.e. one orientated next to the other. Thecompartments may even be orientated in a ‘tyre and rim’ arrangement,i.e. a first compartment is positioned next to a second compartment, butthe first compartment at least partially surrounds the secondcompartment, but does not completely enclose the second compartment.Alternatively one compartment may be completely enclosed within anothercompartment. In such a multicompartment orientation, the firstwater-soluble film according to the present invention may be shaped tocomprise an open compartment into which the detergent or othercomposition is added. The second water-soluble film according to thepresent invention is then laid over the first film in such anorientation as to close the opening of the compartment.

Wherein the unit dose article comprises at least two compartments, oneof the compartments may be smaller than the other compartment. Whereinthe unit dose article comprises at least three compartments, two of thecompartments may be smaller than the third compartment, and preferablythe smaller compartments are superposed on the larger compartment. Thesuperposed compartments preferably are orientated side-by-side.

In a multi-compartment orientation, the composition according to thepresent invention may be comprised in at least one of the compartments.It may for example be comprised in just one compartment, or may becomprised in two compartments, or even in three compartments.

In a multi-compartment orientation, the detergent composition accordingto the present invention may be comprised in at least one of thecompartments. It may for example be comprised in just one compartment,or may be comprised in two compartments, or even in three compartments.

Each compartment may comprise the same or different compositions. Thedifferent compositions could all be in the same form, or they may be indifferent forms.

The water-soluble unit dose article may comprise at least two internalcompartments, wherein a liquid composition is comprised in at least oneof the compartments, preferably wherein the unit dose article comprisesat least three compartments, wherein a liquid composition is comprisedin at least one of the compartments.

A water-soluble unit dose detergent article may comprise at least twointernal compartments, wherein a liquid laundry detergent composition iscomprised in at least one of the compartments, preferably wherein theunit dose article comprises at least three compartments, wherein adetergent composition is comprised in at least one of the compartments.

First and Second Water-Soluble Films

The water-soluble unit dose article comprises a first water-soluble filmand a second water-soluble film and the first water-soluble film and thesecond water-soluble film are chemically different to one another.

For the avoidance of doubt, in the context of the present invention‘chemically different’ herein means where the ‘virgin films’, i.e. filmsreceived from the supplier/manufacture and prior to unwinding on a unitdose article making unit, having at least one substance present in atleast one of the film compositions that differentiates the first fromthe second film composition and impacts at least the water capacity, perthe test method described herein, rendering this at least one physicalfilm property different between the first and second films. Varyingchemical compositions of films due to natural making processes i.e.batch to batch variations are as such not considered chemicallydifferent films within the scope of this invention.

Non limiting examples of chemically differentiating substances includeuse of different polymer target resins and or content, differentplasticizer composition and or content or different surfactant and orcontent. Water soluble unit dose articles comprising films solelydiffering in physical properties but having the same substance contentsuch as films solely differing in film thickness are considered outsidethe scope of this invention. Unit dose articles made from films beingsolely differentiated through the presence versus the absence of acoating layer are also considered outside the scope of the invention.

The first water-soluble film has a first water capacity, and the secondwater-soluble film has a second water capacity wherein the first watercapacity is less than the second water capacity.

The difference between the water capacity of the first water solublefilm and the second water-soluble film is between 0.01% and 1%,preferably from 0.03% to 0.5%, most preferably from 0.05% to 0.3%. Thefirst water-soluble film and the second water-soluble film are describedin more detail below. By ‘difference’ we herein mean the difference inthe value of the first water capacity and the value of the second watercapacity. By ‘water capacity’ we herein mean the capacity of the film toabsorb water over a fixed period of time at a particular relativehumidity and temperature, measured as a mass increase of the film beingtested. The method for measuring water capacity is described in moredetail below.

Preferably, the first water-soluble film has a water capacity from 1% to10%, more preferably from 2% to 8%, most preferably from 3% to 6%.

Preferably, the second water-soluble film has a water capacity from 1.5%to 12%, more preferably from 2.5% to 10%, most preferably from 3.5% to8%.

Preferably, the first water-soluble film is thermoformed duringmanufacture of the unit dose article. By ‘thermoforming’ we herein meanthat the film is heated prior to deformation, e.g. by passing the filmunder an infrared lamp, the deformation step preferably being enabled bylaying the water soluble film over a cavity and applying vacuum or anunder pressure inside the cavity under the film. The secondwater-soluble film may be thermoformed during manufacture of the unitdose article. Alternatively the second water-soluble film may not bethermoformed during manufacture of the unit dose article. Preferably,the first water-soluble film is thermoformed during manufacture of theunit dose article and the second water-soluble film is not thermoformedduring manufacture of the unit dose article.

The first water-soluble film, the second water-soluble film or a mixturethereof independently may have a thickness before incorporation into theunit dose article of between 40 microns and 100 microns, preferablybetween 60 microns and 90 microns, more preferably between 70 micronsand 80 microns.

Preferably the difference in thickness before incorporation into theunit dose article between the first water-soluble film and the secondwater-soluble film is less than 50%, preferably less than 30%, morepreferably less than 20%, even more preferably less than 10%, or thethicknesses may be equal.

The first water-soluble film and the second water-soluble film accordingto the invention are preferably single layer films, more preferablymanufactured via solution casting.

The water-soluble film can further have a residual moisture content ofat least 4 wt. %, for example in a range of about 4 to about 10 wt. %,as measured by Karl Fischer titration.

The first water-soluble film may have a first tensile strain at break ofbetween 300% and 1600%, preferably between 400% and 1200%, morepreferably between 700% and 1200%. The method to determine tensilestrain at break is described in more detail below.

The second water-soluble film may have a second tensile strain at breakof between 300% and 1200%, preferably between 500% and 1000%. By tensilestrain at break we herein mean the ability of the film, pre-equilibratedwith the detergent or other composition contacting the film in a unitdose article comprising said film and composition, to elongate prior tobreaking when a stress is applied. The method to determine tensilestrain at break is described in more detail below.

The difference between the first tensile strain at break and the secondtensile strain at break may be from 10% to 1000%, preferably from 100%to 750%, more preferably from 200% to 500%. By ‘difference in tensilestrain at break’ we herein mean the difference in the value of the firsttensile strain at break and the second tensile strain at break.

Preferably, the first water soluble film has a first elongation modulus,the second water soluble film has a second elongation modulus, the firstelongation modulus is greater than the second elongation modulus, andthe difference between the first elongation modulus and the secondelongation modulus is from a 0.5 MPa to 10 MPa, preferably from 1 MPa to8 MPa, more preferably from 2 MPa to 7 MPa.

By ‘difference’ we herein mean the difference in the value of the firstelongation modulus and the value of the second elongation modulus. By‘elongation modulus’ we herein mean the ability of the film to beelongated when a stress is applied. The method for measuring elongationmodulus is described in more detail below.

Preferably, the first elongation modulus is from 1 MPa to 20 MPa, morepreferably from 3 MPa to 20 MPa.

Preferably, the second elongation modulus is from 1 MPa to 15 MPa, morepreferably from 3 MPa to 15 MPa.

Preferably, the first water soluble film comprises a first water solubleresin and the second water soluble film comprises a second water solubleresin.

Preferably, the first water soluble resin comprises at least onepolyvinyl alcohol or at least one polyvinyl alcohol copolymer or a blendthereof and the second water soluble resin comprises at least onepolyvinyl alcohol or at least one polyvinyl alcohol copolymer or a blendthereof.

The first water soluble resin may comprise a blend of a polyvinylalcohol homopolymer and a polyvinyl alcohol copolymer comprising ananionic monomer unit, optionally wherein the blend comprises from 0% to70% by weight of the first water soluble resin of the polyvinyl alcoholcopolymer comprising an anionic monomer unit and from 30% to about 100%by weight of the first water soluble resin of the polyvinyl alcoholhomopolymer. The blend can comprise from 10% to 70%, or from 15% toabout 65%, or from 20% to 50%, or from 30% to 40% of the polyvinylalcohol copolymer comprising an anionic monomer unit, based on the totalweight of the first water soluble resin. In another type of embodiment,the blend comprises 65 wt. % or greater of an anionic polyvinyl alcoholcopolymer, or greater than 65 wt. % of an anionic polyvinyl alcoholcopolymer.

Polyvinyl alcohol homopolymer means polyvinyl alcohol comprisingpolyvinyl alcohol units and optionally but preferably polyvinyl acetateunits. Polyvinyl alcohol copolymer means a polymer comprising polyvinylalcohol units, optionally but preferably polyvinyl acetate units andanionically modified polyvinyl alcohol units.

The second water soluble resin may comprise a blend of a polyvinylalcohol homopolymer and a polyvinyl alcohol copolymer comprising ananionic monomer unit, optionally wherein the blend comprises from 0% to70% of the polyvinyl alcohol copolymer comprising an anionic monomerunit and from 30% to 100% of the polyvinyl alcohol homopolymer, based onthe total weight of the second water soluble resin in the film. Theblend can comprise from 10% to 70%, or from 15% to 65%, or from 20% to50%, or from 30% to 40% of the polyvinyl alcohol copolymer comprising ananionic monomer unit, based on the total weight of the second watersoluble resin in the film. In another type of embodiment, the blendcomprises 65 wt. % or greater of an anionic polyvinyl alcohol copolymer,or greater than 65 wt. % of an anionic polyvinyl alcohol copolymer.

The anionic monomer unit present in the polyvinyl alcohol copolymer ofthe first resin, present in the polyvinyl alcohol copolymer of thesecond resin, or a mixture thereof may independently be selected fromthe group consisting of anionic monomers derived from of vinyl aceticacid, alkyl acrylates, maleic acid, monoalkyl maleate, dialkyl maleate,monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid,monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethylfumarate, fumaric anhydride, itaconic acid, monomethyl itaconate,dimethyl itaconate, itaconic anhydride, citraconic acid, monoalkylcitraconate, dialkyl citraconate, citraconic anhydride, mesaconic acid,monoalkyl mesaconate, dialkyl mesaconate, mesaconic anhydride,glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate, glutaconicanhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylene sulfonicacid, 2-acrylamido-1-methyl propane sulfonic acid,2-acrylamide-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate,alkali metal salts thereof, esters thereof, and combinations thereof;preferably, wherein the anionic monomer unit is selected from the groupconsisting of anionic monomers derived from maleic acid, monoalkylmaleate, dialkyl maleate, maleic anhydride, alkali metal salts thereof,esters thereof, and combinations thereof; more preferably wherein theanionic monomer unit is selected from the group consisting of anionicmonomers derived from maleic acid, monomethyl maleate, dimethyl maleate,maleic anyhydride, alkali metal salts thereof, esters thereof, andcombinations thereof.

Preferably, the first and second polyvinyl alcohol copolymersindependently comprise from 1 mol % to 8 mol % more preferably from 2mol % to 5 mol %, most preferably from 3 mol % to 4 mol % of the anionicmonomer unit with respect to total polyvinyl alcohol copolymer present.

Preferably, the first polyvinyl alcohol homopolymer and second polyvinylalcohol homopolymer and the first polyvinyl alcohol copolymer and secondpolyvinyl alcohol copolymer independently have a degree of hydrolysis offrom 80% to 99% preferably from 85% to 95% more preferably from 86% and93%.

Preferably, the first polyvinyl alcohol homopolymers and secondpolyvinyl alcohol homopolymer and first polyvinyl alcohol copolymer andsecond polyvinyl alcohol copolymer independently have a 4% solutionviscosity in demineralized water at 25° C. in a range of 4 cP to 40 cP,preferably of 10 cP to 30 cP, more preferably of 12 cP to 25 cP.

Preferably, the first water-soluble film and the second water-solublefilm independently have a water soluble resin content of between 30% and90%, more preferably between 40% and 80%, even more preferably between50% and 75%, most preferably between 60% and 70% by weight of the film.

Other water soluble polymers for use in addition to the first polyvinylalcohol homopolymers and second polyvinyl alcohol homopolymer and firstpolyvinyl alcohol copolymer and second polyvinyl alcohol copolymer caninclude, but are not limited to a vinyl alcohol-vinyl acetate copolymer,sometimes referred to as a PVOH homopolymer, polyacrylates,water-soluble acrylate copolymers, polyvinyl pyrrolidone,polyethyleneimine, pullulan, water-soluble natural polymers including,but not limited to, guar gum, gum Acacia, xanthan gum, carrageenan, andstarch, water-soluble polymer derivatives including, but not limited to,modified starches, ethoxylated starch, hydroxyethylated starch andhydroxypropylated starch, copolymers of the forgoing and combinations ofany of the foregoing. Yet other water-soluble polymers can includepolyalkylene oxides, polyacrylamides, polyacrylic acids and saltsthereof, celluloses, cellulose ethers, cellulose esters, celluloseamides, polyvinyl acetates, polycarboxylic acids and salts thereof,polyaminoacids, polyamides, gelatines, methylcelluloses,carboxymethylcelluloses and salts thereof, dextrins, ethylcelluloses,hydroxyethyl celluloses, hydroxypropyl methylcelluloses, maltodextrins,polymethacrylates, and combinations of any of the foregoing. Suchwater-soluble polymers, whether PVOH or otherwise are commerciallyavailable from a variety of sources.

Preferably, the water-soluble unit dose article exhibits a dissolutionprofile, according to the unit dose article dose article machine washdissolution test method described below of less than 6.2 preferably lessthan 6 more preferably less than 5.8.

The first and or second film may independently be opaque, transparent ortranslucent. The first and or second film may independently comprise aprinted area. The printed area may cover between 10 and 80% of thesurface of the film; or between 10 and 80% of the surface of the filmthat is in contact with the internal space of the compartment; orbetween 10 and 80% of the surface of the film and between 10 and 80% ofthe surface of the compartment.

The area of print may cover an uninterrupted portion of the film or itmay cover parts thereof, i.e. comprise smaller areas of print, the sumof which represents between 10 and 80% of the surface of the film or thesurface of the film in contact with the internal space of thecompartment or both.

The area of print may comprise inks, pigments, dyes, blueing agents ormixtures thereof. The area of print may be opaque, translucent ortransparent.

The area of print may comprise a single colour or maybe comprisemultiple colours, even three colours. The area of print may comprisewhite, black, blue, red colours, or a mixture thereof. The print may bepresent as a layer on the surface of the film or may at least partiallypenetrate into the film. The film will comprise a first side and asecond side. The area of print may be present on either side of thefilm, or be present on both sides of the film. Alternatively, the areaof print may be at least partially comprised within the film itself.

The area of print may be achieved using standard techniques, such asflexographic printing or inkjet printing. Preferably, the area of printis achieved via flexographic printing, in which a film is printed, thenmoulded into the shape of an open compartment. This compartment is thenfilled with a detergent or other composition and a second film placedover the compartment and sealed to the first film. The area of print maybe on either or both sides of the film.

Alternatively, an ink or pigment may be added during the manufacture ofthe film such that all or at least part of the film is coloured.

The first and or second film may independently comprise an aversiveagent, for example a bittering agent. Suitable bittering agents include,but are not limited to, naringin, sucrose octaacetate, quininehydrochloride, denatonium benzoate, or mixtures thereof. Any suitablelevel of aversive agent may be used in the film. Suitable levelsinclude, but are not limited to, 1 to 5000 ppm, or even 100 to 2500 ppm,or even 250 to 2000 ppm.

The first and or second film may also comprise other secondaryingredients typically known by a skilled person in the art such as, butnot limited to, plasticizers, plasticizer compatibilizers, surfactants,lubricants, release agents, fillers, extenders, cross-linking agents,antiblocking agents, antioxidants, detackifying agents, antifoams,nanoparticles such as layered silicate-type nanoclays (e.g., sodiummontmorillonite), bleaching agents (e.g., sodium metabisulfite, sodiumbisulfite or others), aversive agents such as bitterants (e.g.,denatonium salts such as denatonium benzoate, denatonium saccharide, anddenatonium chloride; sucrose octaacetate; quinine; flavonoids such asquercetin and naringen; and quassinoids such as quassin and brucine) andpungents (e.g., capsaicin, piperine, allyl isothiocyanate, andresinferatoxin), and other functional ingredients, in amounts suitablefor their intended purposes. Embodiments including plasticizers arepreferred. The amount of such agents can be up to about 50 wt. %, 20 wt%, 15 wt %, 10 wt %, 5 wt. %, 4 wt % and/or at least 0.01 wt. %, 0.1 wt%, 1 wt %, or 5 wt %, individually or collectively.

The plasticizer can include, but is not limited to, glycerin,diglycerin, sorbitol, ethylene glycol, diethylene glycol, triethyleneglycol, dipropylene glycol, tetraethylene glycol, propylene glycol,polyethylene glycols up to 400 MW, neopentyl glycol, trimethylolpropane,polyether polyols, sorbitol, 2-methyl-1,3-propanediol (MPDiol®),ethanolamines, and a mixture thereof. A preferred plasticizer isglycerin, sorbitol, triethyleneglycol, propylene glycol, dipropyleneglycol, 2-methyl-1,3-propanediol, trimethylolpropane, or a combinationthereof. The total amount of the plasticizer can be in a range of about10 wt. % to about 45 wt. %, or about 15 wt. % to about 35 wt. %, orabout 20 wt. % to about 30 wt. %, or about 20 wt. % to about 45 wt. %,for example about 25 wt. %, based on total film weight. In embodiments,the amount of plasticizer in the water-soluble film is expressed inparts per 100 parts total water soluble polymer (PHR) in thewater-soluble film and is present at least 30 PHR, or at least 35 PHR,for example. The total amount of plasticizer can be up to 40 PHR or 45PHR or 50 PHR, for example. The total amount of plasticizer can be in arange of 30-50 PHR, about 32.5 PHR to about 42.5 PHR, or 35-45 PHR, or35-40 PHR, or greater than 30 PHR and less than 45 PHR, or 40 PHR to 50PHR, for example. The total amount of plasticizer can be 34 or 37.5 PHR.

Surfactants for use in water-soluble films are well known in the art.Optionally, surfactants are included to aid in the dispersion of theresin solution upon casting. Suitable surfactants can include thenonionic, cationic, anionic and zwitterionic classes. Suitablesurfactants include, but are not limited to, polyoxyethylenatedpolyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates,tertiary acetylenic glycols and alkanolamides (nonionics),polyoxyethylenated amines, quaternary ammonium salts and quaternizedpolyoxyethylenated amines (cationics), and amine oxides, N-alkylbetainesand sulfobetaines (zwitterionics). Other suitable surfactants includedioctyl sodium sulfosuccinate, lactylated fatty acid esters of glycerinand propylene glycol, lactylic esters of fatty acids, sodium alkylsulfates, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate80, lecithin, acetylated fatty acid esters of glycerin and propyleneglycol, and acetylated esters of fatty acids, and combinations thereof.In embodiments, the surfactant is selected from the group consisting ofpolyoxyethylenated polyoxypropylene glycols, alcohol ethoxylates,alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides,polyoxyethylenated amines, quaternary ammonium salts and quaternizedpolyoxyethylenated amines, and amine oxides, N-alkylbetaines,sulfobetaines, and combinations thereof.

In various embodiments, the amount of surfactant in the water-solublefilm is in a range of about 0.1 wt % to about 8.0 wt %, or about 1.0 wt% to about 7.0 wt %, or about 3 wt % to about 7 wt %, or about 5 wt % toabout 7 wt %. In embodiments, the amount of surfactant in thewater-soluble film is expressed in parts per 100 parts total watersoluble polymer (phr) in the water-soluble film and is present in arange of about 0.5 phr to about 12 phr, about 1.0 phr to about 11.0 phr,about 3.0 phr to about 10.5 phr, or about 1.0 phr to about 2.0 phr.

Suitable lubricants/release agents can include, but are not limited to,fatty acids and their salts, fatty alcohols, fatty esters, fatty amines,fatty amine acetates and fatty amides. Preferred lubricants/releaseagents are fatty acids, fatty acid salts, and fatty amine acetates. Inone type of embodiment, the amount of lubricant/release agent in thewater-soluble film is in a range of about 0.02 wt % to about 1.5 wt %,optionally about 0.1 wt % to about 1 wt %.

Suitable fillers/extenders/antiblocking agents/detackifying agentsinclude, but are not limited to, starches, modified starches,crosslinked polyvinylpyrrolidone, crosslinked cellulose,microcrystalline cellulose, silica, metallic oxides, calcium carbonate,talc, mica, stearic acid and metal salts thereof, for example, magnesiumstearate. Preferred materials are starches, modified starches andsilica. In one type of embodiment, the amount offiller/extender/antiblocking agent/detackifying agent in the watersoluble film can be in a range of about 1 wt. % to about 6 wt. %, orabout 1 wt. % to about 4 wt. %, or about 2 wt. % to about 4 wt. %, orabout 1 phr to about 6 phr, or about 1 phr to about 4 phr, or about 2phr to about 4 phr, for example.

An anti-block agent (e.g. SiO₂ and/or stearic acid)) can be present inthe film in an amount of at least 0.1 PHR, or at least 0.5 PHR, or atleast 1 PHR, or in a range of about 0.1 to 5.0 PHR, or about 0.1 toabout 3.0 PHR, or about 0.4 to 1.0 PHR, or about 0.5 to about 0.9 PHR,or about 0.5 to about 2 PHR, or about 0.5 to about 1.5 PHR, or 0.1 to1.2 PHR, or 0.1 to 4 PHR, for example 0.5 PHR, 0.6 PHR, 0.7 PHR, 0.8PHR, or 0.9 PHR.

If the anti-block agent is an SiO₂ particle, a suitable median particlesize for the anti-block agent includes a median size in a range of about3 or about 4 microns to about 11 microns, or about 4 to about 8 microns,or about 5 to about 6 microns, for example 5, 6, 7, 8, or 8 microns. Asuitable SiO₂ is an untreated synthetic amorphous silica designed foruse in aqueous systems.

Detergent Composition

The detergent composition may be in the form of free flowing powder, aliquid, a compacted solid, a gel or a mixture thereof.

The detergent composition may be in the form of a free flowing powder.Such a free flowing powder may have an average particle size diameter ofbetween 100 microns and 1500 microns, preferably between 100 microns and1000 microns, more preferably between 100 30 microns and 750 microns.Those skilled in the art will be aware of standard techniques to measureparticle size. The detergent composition may be a free flowing laundrydetergent composition.

The detergent composition may be a liquid. In relation to the liquiddetergent composition of the present invention, the term ‘liquid’encompasses forms such as dispersions, gels, pastes and the like. Theliquid composition may also include gases in suitably subdivided form.However, the liquid composition excludes forms which are non-liquidoverall, such as tablets or granules. The detergent composition may be aliquid laundry detergent composition. The term ‘liquid laundry detergentcomposition’ refers to any laundry detergent composition comprising aliquid capable of wetting and treating fabric e.g., cleaning clothing ina domestic washing machine.

The laundry detergent composition is used during the main wash processbut may also be used as pre-treatment or soaking compositions. Laundrydetergent compositions include fabric detergents, fabric softeners,2-in-1 detergent and softening, pre-treatment compositions and the like.

The laundry detergent composition may comprise an ingredient selectedfrom bleach, bleach catalyst, dye, hueing dye, brightener, cleaningpolymers including alkoxylated polyamines and polyethyleneimines, soilrelease polymer, surfactant, solvent, dye transfer inhibitors, chelant,builder, enzyme, perfume, encapsulated perfume, polycarboxylates,rheology modifiers, structurant, hydrotropes, pigments and dyes,opacifiers, preservatives, anti-oxidants, processing aids, conditioningpolymers including cationic polymers, antibacterial agents, pH trimmingagents such as hydroxides and alkanolamines, suds suppressors, andmixtures thereof.

Surfactants can be selected from anionic, cationic, zwitterionic,non-ionic, amphoteric or 20 mixtures thereof. Preferably, the fabriccare composition comprises anionic, non-ionic or mixtures thereof.

The anionic surfactant may be selected from linear alkyl benzenesulfonate, alkyl ethoxylate sulphate and combinations thereof.

Suitable anionic surfactants useful herein can comprise any of theconventional anionic surfactant types typically used in liquid detergentproducts. These include the alkyl benzene sulfonic acids and their saltsas well as alkoxylated or non-alkoxylated alkyl sulfate materials. Thenon-ionic surfactant may be selected from fatty alcohol alkoxylate, anoxo-synthesised fatty alcohol alkoxylate, Guerbet alcohol alkoxylates,alkyl phenol alcohol alkoxylates or a mixture thereof. Suitable nonionicsurfactants for use herein include the alcohol 30 alkoxylate nonionicsurfactants. Alcohol alkoxylates are materials which correspond to thegeneral formula: R1(CmH2mO)nOH wherein R1 is a C8-C16 alkyl group, m isfrom 2 to 4, and n ranges from about 2 to 12. In one aspect, R1 is analkyl group, which may be primary or secondary, that comprises fromabout 9 to 15 carbon atoms, or from about 10 to 14 carbon atoms. In oneaspect, the alkoxylated fatty alcohols will also be ethoxylatedmaterials that contain on average from about 2 to 12 ethylene oxidemoieties per molecule, or from about 3 to 10 ethylene oxide moieties permolecule.

The shading dyes employed in the present laundry detergent compositionsmay comprise polymeric or non-polymeric dyes, pigments, or mixturesthereof. Preferably the shading dye comprises a polymeric dye,comprising a chromophore constituent and a polymeric constituent. Thechromophore constituent is characterized in that it absorbs light in thewavelength range of blue, red, violet, purple, or combinations thereofupon exposure to light. In one aspect, the chromophore constituentexhibits an absorbance spectrum maximum from about 520 nanometers toabout 640 nanometers in water and/or methanol, and in another aspect,from about 560 nanometers to about 610 nanometers in water and/ormethanol.

Although any suitable chromophore may be used, the dye chromophore ispreferably selected from benzodifuranes, methine, triphenylmethanes,napthalimides, pyrazole, napthoquinone, anthraquinone, azo, oxazine,azine, xanthene, triphenodioxazine and phthalocyanine dye chromophores.Mono and di-azo dye chromophores are preferred.

The dye may be introduced into the detergent composition in the form ofthe unpurified mixture that is the direct result of an organic synthesisroute. In addition to the dye polymer therefore, there may also bepresent minor amounts of un-reacted starting materials, products of sidereactions and mixtures of the dye polymers comprising different chainlengths of the repeating units, as would be expected to result from anypolymerisation step.

The laundry detergent compositions can comprise one or more detergentenzymes which provide cleaning performance and/or fabric care benefits.Examples of suitable enzymes include, but are not limited to,hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases,phospholipases, esterases, cutinases, pectinases, keratanases,reductases, oxidases, phenoloxidases, lipoxygenases, ligninases,pullulanases, tannases, pentosanases, malanases, β-glucanases,arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, ormixtures thereof. A typical combination is a cocktail of conventionalapplicable enzymes like protease, lipase, cutinase and/or cellulase inconjunction with amylase.

The laundry detergent compositions of the present invention may compriseone or more bleaching agents. Suitable bleaching agents other thanbleaching catalysts include photobleaches, bleach activators, hydrogenperoxide, sources of hydrogen peroxide, pre-formed peracids and mixturesthereof.

The detergent composition may comprise a brightener. Suitablebrighteners are stilbenes, such as brightener 15. Other suitablebrighteners are hydrophobic brighteners, and brightener 49. Thebrightener may be in micronized particulate form, having a weightaverage particle size in the range of from 3 to 30 micrometers, or from3 micrometers to 20 micrometers, or from 3 to 10 micrometers. Thebrightener can be alpha or beta crystalline form.

The detergent compositions herein may also optionally contain one ormore copper, iron and/or manganese chelating agents. The chelant maycomprise 1-hydroxyethanediphosphonic acid (HEDP) and salts thereof;N,N-dicarboxymethyl-2-aminopentane-1,5-dioic acid and salts thereof;2-phosphonobutane-1,2,4-tricarboxylic acid and salts thereof; and anycombination thereof.

The detergent compositions of the present invention may also include oneor more dye transfer inhibiting agents. Suitable polymeric dye transferinhibiting agents include, but are not limited to, polyvinylpyrrolidonepolymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidoneand N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles ormixtures thereof.

The laundry detergent composition may comprise one or more polymers.Suitable polymers include carboxylate polymers, polyethylene glycolpolymers, polyester soil release polymers such as terephthalatepolymers, amine polymers, cellulosic polymers, dye transfer inhibitionpolymers, dye lock polymers such as a condensation oligomer produced bycondensation of imidazole and epichlorhydrin, optionally in ratio of1:4:1, hexamethylenediamine derivative polymers, and any combinationthereof.

Other suitable cellulosic polymers may have a degree of substitution(DS) of from 0.01 to 0.99 and a degree of blockiness (DB) such thateither DS+DB is of at least 1.00 or DB+2DS-DS2 is at least 1.20. Thesubstituted cellulosic polymer can have a degree of substitution (DS) ofat least 0.55. The substituted cellulosic polymer can have a degree ofblockiness (DB) of at least 0.35. The substituted cellulosic polymer canhave a DS+DB, of from 1.05 to 2.00. A suitable substituted cellulosicpolymer is carboxymethylcellulose.

Another suitable cellulosic polymer is cationically modifiedhydroxyethyl cellulose.

Suitable perfumes include perfume microcapsules, polymer assistedperfume delivery systems including Schiff base perfume/polymercomplexes, starch-encapsulated perfume accords, perfume-loaded zeolites,blooming perfume accords, and any combination thereof. A suitableperfume microcapsule is melamine formaldehyde based, typicallycomprising perfume that is encapsulated by a shell comprising melamineformaldehyde. It may be highly suitable for such perfume microcapsulesto comprise cationic and/or cationic precursor material in the shell,such as polyvinyl formamide (PVF) and/or cationically modifiedhydroxyethyl cellulose (catHEC).

Suitable suds suppressors include silicone and/or fatty acid such asstearic acid.

The laundry detergent composition maybe coloured. The colour of theliquid laundry detergent composition may be the same or different to anyprinted area on the film of the article. Each compartment of the unitdose article may have a different colour. Preferably, the liquid laundrydetergent composition comprises a non-substantive dye having an averagedegree of alkoxylation of at least 16.

Other Compositions

The composition for use inside the unit dose article may be anon-detergent composition and/or a non-household care composition. Afabric or household care composition includes fabric treatments, hardsurfaces, air care, car care, dishwashing, fabric conditioning andsoftening, laundry detergency, laundry and rinse additive and/or care,hard surface cleaning and/or treatment, and other cleaning for consumeror institutional use. Non-household care compositions are for otheruses. For example, a non-household care composition can be selected fromagricultural compositions, aviation compositions, food and nutritivecompositions, industrial compositions, livestock compositions, marinecompositions, medical compositions, mercantile compositions, militaryand quasi-military compositions, office compositions, and recreationaland park compositions, pet compositions, water-treatment compositions,including cleaning and detergent compositions applicable to any such useuse while excluding fabric and household care compositions.

It is contemplated that one type of embodiment will include an articleas described herein with a sealed compartment containing a fabric careor household care composition, a film including a blend of a polyvinylalcohol homopolymer and an anionic polyvinyl alcohol copolymer, and boththe first water soluble film and the second water soluble film includeblends include 65 wt. % or greater of an anionic polyvinyl alcoholcopolymer.

It is contemplated that another type of embodiment will include anarticle as described herein with a sealed compartment containing afabric care or household care composition, a film including a blend ofat least two anionic polyvinyl alcohol copolymers, and both then firstwater soluble film and the second water soluble film include blends ofat least two anionic polyvinyl alcohol copolymers.

In one type of embodiment, the composition can include an agrochemical,e.g. one or more insecticides, fungicides, herbicides, pesticides,miticides, repellants, attractants, defoliaments, plant growthregulators, fertilizers, bactericides, micronutrients, and traceelements. Suitable agrochemicals and secondary agents are described inU.S. Pat. Nos. 6,204,223 and 4,681,228 and EP 0989803 A1. For example,suitable herbicides include paraquat salts (for example paraquatdichloride or paraquat bis(methylsulphate), diquat salts (for examplediquat dibromide or diquat alginate), and glyphosate or a salt or esterthereof (such as glyphosate isopropylammonium, glyphosate sesquisodiumor glyphosate trimesium, also known as sulfosate). Incompatible pairs ofcrop protection chemicals can be used in separate chambers, for exampleas described in U.S. Pat. No. 5,558,228. Incompatible pairs of cropprotection chemicals that can be used include, for example, bensulfuronmethyl and molinate; 2,4-D and thifensulfuron methyl; 2,4-D and methyl2-[[[[N-4-methoxy-6-methyl-1,3,5-triazine-2-yl)-N-methylamino]carbonyl]amino]-sulfonyl]benzoate;2,4-D and metsulfuron methyl; maneb or mancozeb and benomyl; glyphosateand metsulfuron methyl; tralomethrin and any organophosphate such asmonocrotophos or dimethoate; bromoxynil andN-[[4,6-dimethoxypyrimidine-2-yl)-amino]carbonyl]-3-(ethylsulfonyl)-2-pyridine-sulfonamide;bromoxynil and methyl2-[[[[(4-methyl-6-methoxy)-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-benzoate;bromoxynil and methyl2-[[[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]carbonyl]amino]-sulfonyl]benzoate.In another, related, type of embodiment, the composition can include oneor more seeds, optionally together with soil, and further optionallytogether with one or more additional components selected from mulch,sand, peat moss, water jelly crystals, and fertilizers, e.g. includingtypes of embodiments described in U.S. Pat. No. 8,333,033.

In another type of embodiment, the composition is a water-treatmentagent. Such agents include aggressive oxidizing chemicals, e.g. asdescribed in U.S. Patent Application Publication No. 2014/0110301 andU.S. Pat. No. 8,728,593. For example, sanitizing agents can includehypochlorite salts such as sodium hypochlorite, calcium hypochlorite,and lithium hypochlorite; chlorinated isocyanurates such asdichloroisocyanuric acid (also referred to as “dichlor” ordichloro-s-triazinetrione, 1,3-dichloro-1,3,5-triazinane-2,4,6-trione)and trichloroisocyanuric acid (also referred to as “trichlor” or1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione). Salts and hydrates ofthe sanitizing compounds are also contemplated. For example,dichloroisocyanuric acid may be provided as sodium dichloroisocyanurate,sodium dichloroisocyanurate acid dihydrate, among others. Brominecontaining sanitizing agents may also be suitable for use in unit dosepackaging applications, such as 1,3-dibromo-5,5-dimethylhydantoin(DBDMH), 2,2-dibromo-3-nitrilopropionamide (DBNPA), dibromocyano aceticacid amide, 1-bromo-3-chloro-5,5-dimethylhydantoin; and2-bromo-2-nitro-1,3-propanediol, among others. The oxidizing agent canbe one described in U.S. Pat. No. 7,476,325, e.g. potassium hydrogenperoxymonosulfate. The composition can be a pH-adjusting chemical, e.g.as described in U.S. Patent Application Publication No. 2008/0185347,and can include, for example, an acidic component and an alkalinecomponent such that the composition is effervescent when contacted withwater, and adjusts the water pH. Suitable ingredients include sodiumbicarbonate, sodium bisulfate, potassium hydroxide, sulfamic acid,organic carboxylic acids, sulfonic acids, and potassium dihydrogenphosphate. A buffer blend can include boric acid, sodium carbonate,glycolic acid, and oxone monopersulfate, for example.

A water-treatment agent can be or can include a flocculant, e.g. asdescribed in U.S. Patent Application Publication No. 2014/0124454. Theflocculant can include a polymer flocculant, e.g. polyacrylamide, apolyacrylamide copolymer such as an acrylamide copolymers ofdiallydimethylammonium chloride (DADMAC), dimethylaminoethylacrylate(DMAEA), dimethylaminoethylmethacrylate (DMAEM),3-methylamidepropyltrimethylammonium chloride (MAPTAC) or acrylic acid;a cationic polyacrylamide; an anionic polyacrylamide; a neutralpolyacrylamide; a polyamine; polyvinylamine; polyethylene imine;polydimethyldiallylammonium chloride; poly oxyethylene; polyvinylalcohol; polyvinyl pyrrolidone; polyacrylic acid; polyphosphoric acid;polystyrene sulfonic acid; or any combination thereof. A flocculant canbe selected from chitosan acetate, chitosan lactate, chitosan adipate,chitosan glutamate, chitosan succinate, chitosan malate, chitosancitrate, chitosan fumarate, chitosan hydrochloride, and combinationsthereof. The water-treating composition can include a phosphate removingsubstance, e.g. one or more selected from a zirconium compound, a rareearth lanthanide salt, an aluminum compound, an iron compound, or anycombination thereof.

The composition can be a limescale removing composition, e.g. citric ormaleic acid or a sulphate salt thereof, or any mixture thereof, e.g. asdescribed in U.S. Patent Application No. 2006/0172910.

Various other types of compositions are contemplated for use in the unitdose articles described herein, including particulates, for example downfeathers, e.g. as described in U.S. RE29059 E; super absorbent polymers,e.g. as described in U.S. Patent Application Publication Nos.2004/0144682 and 2006/0173430; pigments and tinters, e.g. as describedin U.S. Pat. No. 3,580,390 and U.S. Patent Application Publication No.2011/0054111; brazing flux (e.g. alkali metal fluoroaluminates, alkalimetal fluorosilicates and alkali metal fluorozincates), e.g. asdescribed in U.S. Pat. No. 8,163,104; food items (e.g., coffee powder ordried soup) as described in U.S. Patent Application Publication No.2007/0003719; and wound dressings, e.g. as described in U.S. Pat. No.4,466,431.

At least one compartment of the unit dose article may comprise a solid.If present, the solid may be present at a concentration of at least 5%by weight of the unit dose article.

Method of Making a Unit Dose Article

Those skilled in the art will be aware of processes to make thedetergent and non-detergent compositions of the present invention. Thoseskilled in the art will be aware of standard processes and equipment tomake the detergent and other compositions.

Those skilled in the art will be aware of standard techniques to makethe unit dose article according to any aspect of the present invention.Standard forming processes including but not limited to thermoformingand vacuum forming techniques may be used.

A preferred method of making the water-soluble unit dose articleaccording to the present invention comprises the steps of moulding thefirst water-soluble film in a mould to form an open cavity, filling thecavity with the detergent or other composition, laying the second filmover the first film to close the cavity, and sealing the first andsecond films together preferably through solvent sealing, the solventpreferably comprising water, to produce the water-soluble unit dosearticle.

All ranges set forth herein include all possible subsets of ranges andany combinations of such subset ranges. By default, ranges are inclusiveof the stated endpoints, unless stated otherwise. Where a range ofvalues is provided, it is understood that each intervening value betweenthe upper and lower limit of that range and any other stated orintervening value in that stated range, is encompassed within thedisclosure. The upper and lower limits of these smaller ranges mayindependently be included in the smaller ranges, and are alsoencompassed within the disclosure, subject to any specifically excludedlimit in the stated range. Where the stated range includes one or bothof the limits, ranges excluding either or both of those included limitsare also contemplated to be part of the disclosure.

It is expressly contemplated that for any number value described herein,e.g. as a parameter of the subject matter described or part of a rangeassociated with the subject matter described, an alternative which formspart of the description is a functionally equivalent range surroundingthe specific numerical value (e.g. for a dimension disclosed as “40 mm”an alternative embodiment contemplated is “about 40 mm”).

Test Protocols

Unit Dose Article Machine Wash Dissolution Test Method

This method is designed to assess the relative dissolution properties oflaundry water soluble unit dose articles under stressed washing machineconditions. For this method Electrolux

Programmable Washing machines type W565H, an adjusted EMPA221 load(EMPA221 source: Swissatest—SWISSatest testsmaterials, Movenstrasse 12CH9015 St Gallen, Switzerland) and Digieye picture taking equipment(Digieye by VeriVide) were used.

The adjusted EMPA221 load was prepared by coloring the load into anorange color by using commercially available dying solutions for inwashing machines dying (Dylon goldfish orange washing machine dye (N°55)). To color the load any standard household washing machine can beused, employing a standard cotton cycle at 40° C. 500 g of salt and 200g of the Dylon goldfish orange machine dye are added to the drum of thewashing machine. The drum was consequently moved to the left and theright until the salt and the dye were not visible anymore. 25 EMPA 221items (size of 50 cm×50 cm, overlocked on the edges to prevent fraying),were consequently evenly distributed over the drum without folding ofthe items. A standard cotton cycle at 40° C. was run at a water hardnessof 15 gpg. After completion of the cycle 50 g of Ariel Sensitive powderwas added into the dispenser and a normal cotton cycle at 40° C. was runat a water hardness of 15 gpg. After completion of this cycle 2additional normal cotton cycles at 40° C. without any detergent were runat a water hardness of 15 gpg, followed by line-drying the items. Tonote: Brand new EMPA221 items must be desized before coloring them byadding 25 items into a front loading Miele washing machine and running 2short cotton cycles at 60° C. (approximate duration of 1 h30) with 50 gof Ariel sensitive powder and a water hardness of 15 gpg, followed byrunning 2 more short cotton cycles at 60° C. (approximate duration of 1h30) with no detergent and a water hardness of 15 gpg, followed bytumble drying.

The Electrolux W565 programmable washing machines were programmed with 2programs. The first program was designed to equally wet the load(pre-wet program). The second program (dissolution program) was utilizedto simulate 10 min of a Western Europe stressed cycle setting, followedby pumping out the water and starting a spin of 3 min at 1100 rpm.

Pre-wet program Dissolution program Wash Time 5 min 10 min Motorrotation 49 rpm 40 rpm Water intake 12 L 4 L Heating No heating Noheating Motor action time 28 s 28 s Motor resting time 12 s 12 s Motoraction time 28 s 28 s Counterclockwi Drain Draining time 20 s 20 s Motorrotation 20 rpm 49 rpm Extraction Time NA 3 min Motor rotation NA 1100rpm

A load consisting of 50 dyed EMPA221 fabrics (ca. 2.45 kg) was evenlyintroduced in the Electrolux W565 washing machine and the pre-wetprogram was started. After the pre-wet program, 6 water soluble unitdose articles were distributed evenly across the wet load, after whichthe dissolution program was initiated. At the end of the full program,the wet load was trasnferred to a grading room (equipped with D65lighting conditions) to be assessed for residues by expert graders. Eachfabric which had discoloration spots due to remnant detergent or excessPVA, was selected out of the load for image analysis.

This image analysis was conducted by acquiring pictures of each side ofthe selected fabrics using the Digi-Eye camera (setting: “d90 DiffuseLight. Shutter time ¼. Aperture 8”). The fabrics should be put onto agray or black background to enhance the contrast. After this the imagewas assessed through image analysis software to calculate the total sizeof residue detected in the load (pixel count). This tool detectsresidues by identifying spots that are of a different color than thenormal ballast, using delta E thresholding (delta E of 6). For onemachine and load a residue score is then calculated by summing the totalarea of residues present in the load. The logarithmic value of the totalresidue area is calculated and the average of 4 external replicates,i.e. 4 different washing machine runs, was reported.

Unit Dose Article Seal Failure Test Method

This test method describes the practice for determining unit dosearticle seal failure using the Instron Universal Materials Testinginstrument (Instron Industrial Products, 825 University Ave., Norwood,Mass. 02062-2643) with a load cell of maximum 100 kN (kilo Newton). Viacompression of a unit dose article, this method determines the sealfailure of the unit dose article by putting pressure on the film andseal regions. Unit dose articles opening at the seal area at a pressurelower than 250N are reported as seal failures.

The unit dose article seal failure was measured no sooner than one hourafter unit dose article production so that the film/unit dose articleshad time to set after converting. The method was performed in a roomenvironment between 30% and 40% relative humidity (RH) and between 20°C. and 23° C. Stored unit dose articles were allowed to re-equilibrateto the testing room environment for one hour prior to testing.

FIG. 1 . shows a schematic illustration of the basic configuration ofthe unit dose article seal failure test. To measure unit dose articleseal failure, a unit dose article 510 was enclosed in a plasticde-aerated bag 500 (150 mm by 124 mm with closure, 60 micron thick—e.g.Raja grip RGP6B) to prevent contamination of working environment uponunit dose article rupture. After enclosure in the bag, the unit dosearticle 510 was centered between two compression plates 520, 530 of theinstrument. The unit dose article 510 was placed in an upright position,so that the width seal dimension 540 (e.g. smallest dimension within adefined rectangular plane just encompassing the seal area, 41 mm inactual unit dose articles tested) was between the compression plates(x-direction) such that the stress was applied on the width seal. Forthe compression, the speed of decreasing the distance between the plates520 and 530 is set at 60 mm/min. Ten replicates were conducted per testleg, and number of seal failed unit dose articles, i.e. opening at theseal area at a pressure lower than 250N, are reported.

Method for Measurement of Water Capacity

Water capacity was measured with a DVS (Dynamic Vapor Sorption)Instrument. The instrument used was a SPS-DVS (model SPSx-1μ-High loadwith permeability kit) from ProUmid. The DVS uses gravimetry fordetermination of moisture sorption/desorption and is fully automated.

The accuracy of the system is ±0.6% for the RH (relative humidity) overa range of 0-98% and ±0.3° C. at a temperature of 25° C. The temperaturecan range from +5 to +60° C. The microbalance in the instrument iscapable of resolving 0.1 μg in mass change. Two replicates of each filmare measured and the average water capacity value is reported.

For the specific conditions of the test, a 6 pan carousel which allowsto test 5 films simultaneously (1 pan is used as a reference for themicrobalance and needs to remain empty) was used.

Each pan has an aluminum ring with screws, designed to fix the films. Apiece of film was placed onto a pan and after gentle stretching, thering was placed on top and the film was tightly fixed with the screwsand excess film removed. The film covering the pan surface had an 80 mmdiameter.

The temperature was fixed at 20° C. Relative humidity (RH) was set at35% for 6 hours, and then gradually raised onto 50% in 5 min. The RHremained at 50% for 12 hours. The total duration of the measurement was18 hours.

The cycle time (=time between measuring each pan) was set to 10 min andthe DVS records each weight result vs. time and calculates automaticallythe % Dm (relative mass variation versus starting weight of the film,i.e. 10% reflects a 10% film weight increase versus starting filmweight).

The water capacity (or % Dm gained over 50% RH cycle during the fixedtime of 12 hours at 20° C.) was calculated by difference of the value %Dm at 50% RH (last value measured at 50% RH) minus % Dm at 35% RH (lastvalue before going up to 50% RH).

Tensile Strain Test and e-Modulus Test

A water-soluble film characterized by or to be tested for tensile strainaccording to the Tensile Strain (TS) Test and e-modulus (elongationmodulus or tensile stress) according to the Modulus (MOD) Test wasanalyzed as follows. The procedure includes the determination of tensilestrain and the determination of e-modulus according to ASTM D 882(“Standard Test Method for Tensile Properties of Thin PlasticSheeting”). An INSTRON tensile testing apparatus (Model 5544 TensileTester or equivalent—Instron Industrial Products, 825 University Ave.,Norwood, Mass. 02062-2643) was used for the collection of film data. Aminimum of three test specimens, each cut with reliable cutting tools(e.g. JDC precision sample cutter, Model 1-10, from Thwing AlbertInstrument Company, Philadelphia, Pa. U.S.A.) to ensure dimensionalstability and reproducibility, were tested in the machine direction (MD)(where applicable), i.e. water soluble film roll winding/unwindingdirection, for each measurement. Water soluble films werepre-conditioned to testing environmental conditions for a minimum of 48h. Tests were conducted in the standard laboratory atmosphere of 23±2.0°C. and 35±5% relative humidity. For tensile strain or modulusdetermination, 1″-wide (2.54 cm) samples of a single film sheet having athickness of 3.0±0.15 mil (or 76.2±3.8 μm) are prepared. For e-modulustesting virgin films were tested. For tensile strain testing test filmswere first pre-immersed in testing detergent according to the protocoldescribed below. The sample was then transferred to the INSTRON tensiletesting machine to proceed with testing. The tensile testing machine wasprepared according to manufacturer instructions, equipped with a 500 Nload cell, and calibrated. The correct grips and faces were fitted(INSTRON grips having model number 2702-032 faces, which are rubbercoated and 25 mm wide, or equivalent). The samples were mounted into thetensile testing machine, elongated at a rate of 1N/min, and analyzed todetermine the e-modulus (i.e., slope of the stress-strain curve in theelastic deformation region) and tensile strain at break (i.e., %elongation achieved at the film break, i.e. 100% reflects startinglength, 200% reflects a film that has been lengthened 2 times at filmbreak). The average of minimum three test specimens was calculated andreported.

Film Pre-Immersion Protocol

A film sample measuring 11 cm by 12 cm was prepared of both filmsintended to be used to form a sealed compartment enclosing a liquidhousehold detergent composition. A total of 750 ml of the householdliquid detergent composition intended to be enclosed within a sealedcompartment comprising the test films, was required for each test film.The bottom of a clean inert glass recipient was covered with a thinlayer of liquid and the film to be tested was spread on the liquid; airbubbles trapped under the film were gently pushed towards the sides. Theremaining liquid was then gently poured on top of the film, in such away that the film was fully immersed into the liquid. The film shouldremain free of wrinkles and no air bubbles should be in contact with thefilm. The film stayed in contact with the liquid and was stored underclosed vessel conditions for 6 days at 35° C. and 1 night at 21° C. Aseparate glass recipient was used for each test film. The film was thenremoved from the storage vessel, and the excess liquid was removed fromthe film. A piece of paper was put on the film which was laid on top ofa bench paper, and then the film was wiped dry thoroughly with drypaper. Films were consequently pre-conditioned to tensile strainenvironmental testing conditions as described above. When intendingenclosing solid household detergent compositions, virgin films were usedfor tensile strain testing.

EXAMPLES

The following unit dose articles were prepared and tested for unit dosearticle seal strength per the protocol described herein. Comparativeunit dose articles outside the scope of the invention have been preparedout of a single film type while example unit dose articles according tothe invention were prepared out of two different films, differing inwater capacity value according to the invention.

Multicompartment water soluble unit dose articles with a 41 mm×43 mmfootprint, cavity depth of 20.1 mm and cavity volume of 25 ml, were madethrough thermo/vacuum forming. For dual film example unit dose articlefilms A and C were deformed under vacuum while films B and D were usedas closing films respectively. A standard detergent composition, ascommercially available in the UK in January 2016 in the bottomcompartment of Fairy non-Bio 3-in-1 water soluble unit dose articlesproduct were enclosed inside these unit dose articles.

Table 1 below details film compositions used to prepare comparative andexample unit dose articles.

TABLE 1 Polymer 2 Starting film Resin Polymer 1 (anionic-PVOH copolymer)(PVOH homopolymer) thickness = 76 content Blend Anionic Anionic 4% 4%micron in film ratio source substitution dH viscosity dH viscosityExample 1 Comparative Film 65% 30/70 Monomethyl 4% 89% 16 cps 87% 13 cpspouch 1 B maleate (single film (carboxylated) type = B) Example Film 65%40/60 Monomethyl 4% 89% 16 cps 87% 24 cps pouch 1 A maleate (dual film(carboxylated) type = A + B) Film 65% 30/70 Monomethyl 4% 89% 16 cps 87%13 cps B maleate (carboxylated) Example 2 Comparative Film 65% 30/70Monomethyl 4% 89% 16 cps 88% 12 cps pouch 2 D maleate (single film(carboxylated) type = D) Example Film 65% 30/70 Monomethyl 4% 89% 16 cps88% 17 cps pouch 2 C maleate (dual film (carboxylated) type = C + D)Film 65% 30/70 Monomethyl 4% 89% 16 cps 88% 12 cps D maleate(carboxylated)

Table 2 below details physical properties of the respective films usedin the examples.

TABLE 2 Water capacity e-modulus Tensile strain at break Film A 5.058% 11.4 MPa 1123%  Film B 5.141%  8.25 MPa 855% Film C 4.259% 19.35 MPa906% Film D 4.406% 14.29 MPa 555%

From Table 3 below it is clear that the unit dose articles 1 and 2 madeof 2 films differing in water capacity according to the scope of theinvention provide both good seal strength, compared to respectivecomparative examples 1 and 2 made out of a single type film.

TABLE 3 Seal Failures Example1 Comparative article 1 1 Article 1 0Example 2 Comparative article 2 2 Article 2 0

From Table 4 below it is clear that the wash process comprising theexample unit dose articles 1 and 2 made of 2 films differing in watercapacity according to the scope of the invention provides reduced fabricresidues for the wash as compared to a wash process comprising thecomparative examples 1, 2, 3 and 4 made out of a single type film.

Article Avg Log(residue area) Example 1 Comparative article 1 6.4Comparative article 2 6.5 article 1 5.7 Example 2 Comparative article 36.3 Comparative article 4 6.3 article 2 5.7

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A water-soluble unit dose article comprising afirst water-soluble film comprising a first water soluble resin, whereinthe first water soluble resin comprises a blend of polyvinyl alcohol(PVOH) polymers; and a second water-soluble film comprising a secondwater soluble resin, wherein the second water soluble resin comprises ablend of PVOH polymers; and, optionally comprising a compositioncontained within the unit dose article, wherein the first water-solublefilm and the second water-soluble film are sealed together along a sealarea, in order to improve the seal strength in the seal area; whereinthe first water-soluble film and the second water-soluble film arechemically different to one another, wherein the first water-solublefilm has a first water capacity and a first tensile strain at break, andwherein the second water-soluble film has a second water capacity and asecond tensile strain at break, wherein the first water capacity is lessthan the second water capacity, and wherein the difference between thewater capacity of the first water soluble film and the secondwater-soluble film is in a range of 0.01% and 1%, wherein the firsttensile strain at break is greater than the second tensile strain atbreak, and the difference between the first tensile strain at break andthe second tensile strain at break is in a range of 10% to 1000%;provided that when the composition is a fabric care or household carecomposition and a film comprises a blend of a polyvinyl alcoholhomopolymer resin and an anionic polyvinyl alcohol copolymer resin, thenboth the first water soluble film and the second water soluble filmcomprise blends that include 65 wt. % or greater of an anionic polyvinylalcohol copolymer resin; and provided that when the composition is afabric care or household care composition and a film comprises a blendof at least two anionic polyvinyl alcohol copolymer resins, then boththe first water soluble film and the second water soluble film compriseblends of at least two anionic polyvinyl alcohol copolymer resins. 2.The water-soluble unit dose article according to claim 1, wherein thefirst water-soluble film has a water capacity in a range of 1% to 10%.3. The water-soluble unit dose article according to claim 2, wherein thefirst water-soluble film has a water capacity in a range of 3% to 6%. 4.The water-soluble unit dose article according to claim 2, wherein thesecond water-soluble film has a water capacity in a range of 1.5% to12%.
 5. The water-soluble unit dose article according to claim 1,wherein the difference in water capacity is in a range of 0.03% to 0.5%.6. The water-soluble unit dose article according to claim 1, wherein thefirst water soluble resin comprises a blend of a polyvinyl alcoholhomopolymer and a polyvinyl alcohol copolymer comprising an anionicmonomer unit.
 7. The water-soluble unit dose article according to claim6, wherein the second water soluble resin comprises a blend of apolyvinyl alcohol homopolymer and a polyvinyl alcohol copolymercomprising an anionic monomer unit.
 8. The water-soluble unit dosearticle according to claim 7, wherein the first water soluble resincomprises from 65% by weight or greater of the first water soluble resinof the polyvinyl alcohol copolymer comprising an anionic monomer unitand the second water soluble resin comprises from 65% by weight orgreater of the second water soluble resin of the polyvinyl alcoholcopolymer comprising an anionic monomer unit.
 9. The water-soluble unitdose article according to claim 8, wherein the anionic monomer unit isderived from a monomer selected from the group consisting of vinylacetic acid, alkyl acrylates, maleic acid, monoalkyl maleate, dialkylmaleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaricacid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate,dimethyl fumarate, fumaric anhydride, itaconic acid, monomethylitaconate, dimethyl itaconate, itaconic anhydride, citraconic acid,monoalkyl citraconate, dialkyl citraconate, citraconic anhydride,mesaconic acid, monoalkyl mesaconate, dialkyl mesaconate, mesaconicanhydride, glutaconic acid, monoalkyl glutaconate, dialkyl glutaconate,glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylenesulfonic acid, 2-acrylamido-1-methyl propane sulfonic acid,2-acrylamido-2-methylpropanesulfonic acid,2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate,alkali metal salts thereof, esters thereof, and combinations thereof.10. The water-soluble unit dose article according to claim 1, whereinthe first water-soluble film, and the second water-soluble filmindependently have a thickness before incorporation into the unit dosearticle in a range of 40 microns to 100 microns.
 11. The water-solubleunit dose article according to claim 1, wherein the first water-solublefilm has a first tensile strain at break in a range of 300% to 1600% andthe second water-soluble film has a second tensile strain at break in arange of 300% to 1200%.
 12. The water-soluble unit dose articleaccording to claim 1, wherein the PVOH polymers of the first watersoluble resin and the second water soluble resin each have a degree ofhydrolysis in a range of 80% to 99%.
 13. The water-soluble unit dosearticle according to claim 12, wherein the PVOH polymers of the firstwater soluble resin and the second water soluble resin each have adegree of hydrolysis in a range of 85% to 95%.
 14. The water-solubleunit dose article according to claim 13, wherein the PVOH polymers ofthe first water soluble resin and the second water soluble resin eachhave a degree of hydrolysis in a range of 86% to 93%.
 15. A unit dosearticle comprising at least a first water-soluble film, a secondwater-soluble film and optionally a composition contained within theunit dose article, wherein the first water-soluble film and the secondwater-soluble film are according to claim 1, provided that when thecomposition is a fabric care or household care composition and a filmcomprises a blend of a polyvinyl alcohol homopolymer resin and ananionic polyvinyl alcohol copolymer resin, then both the first watersoluble film and the second water soluble film comprise blends thatinclude 65 wt. % or greater of an anionic polyvinyl alcohol copolymerresin; and provided that when the composition is a fabric care orhousehold care composition and a film comprises a blend of at least twoanionic polyvinyl alcohol copolymer resins, then both the first watersoluble film and the second water soluble film comprise blends of atleast two anionic polyvinyl alcohol copolymer resins.
 16. The unit dosearticle according to claim 15, wherein the unit dose article comprises adetergent composition contained within the unit dose article.
 17. Theunit dose article according to claim 16, wherein the unit dose articleis disposed in a storage receptacle.
 18. The unit dose article accordingto claim 17, wherein the storage receptacle is a flexible, optionallyresealable, bag, a rigid, optionally recloseable, tub or a mixturethereof, optionally, wherein the storage receptacle comprises a childresistant closure.
 19. The unit dose article according to claim 15,wherein the unit dose article contains a non-household care compositioncontained within the unit dose article.
 20. The unit dose articleaccording to claim 19, wherein the non-household care composition isselected from agricultural compositions, aviation compositions, food andnutritive compositions, industrial compositions, livestock compositions,marine compositions, medical compositions, mercantile compositions,military and quasi-military compositions, office compositions, andrecreational and park compositions, pet compositions, water-treatmentcompositions.
 21. The unit dose article according to claim 20, whereinthe non-household care composition comprises an agriculturalcomposition.
 22. The unit dose article according to claim 20, whereinthe non-household care composition comprises a water-treatmentcomposition.
 23. A water-soluble unit dose article comprising a firstwater-soluble film comprising a first water soluble resin, wherein thefirst water soluble resin comprises a blend of PVOH polymers, whereinthe blend of PVOH polymers comprises a PVOH homopolymer that has a 4%solution viscosity in demineralized water at 25° C. in a range of 4 cPto 40 cP and a degree of hydrolysis of 86% to 93%; a secondwater-soluble film comprising a second water soluble resin, wherein thesecond water soluble resin comprises a blend of PVOH polymers, whereinthe blend of PVOH polymers comprises a PVOH homopolymer that has a 4%solution viscosity in demineralized water at 25° C. in a range of 4 cPto 40 cP and a degree of hydrolysis in a range of 86% to 93%; and, acomposition contained within the unit dose article, wherein the firstwater-soluble film and the second water-soluble film are sealed togetheralong a seal area, in order to improve the seal strength in the sealarea; wherein the first water-soluble film and the second water-solublefilm are chemically different to one another, wherein the firstwater-soluble film has a first water capacity and a first tensile strainat break, and wherein the second water-soluble film has a second watercapacity and a second tensile strain at break, wherein the first watercapacity is less than the second water capacity, and wherein thedifference between the water capacity of the first water soluble filmand the second water-soluble film is in a range of 0.01% to 1%, whereinthe first tensile strain at break is greater than the second tensilestrain at break, and the difference between the first tensile strain atbreak and the second tensile strain at break is in a range of 10% to1000%; provided that when the composition is a fabric care or householdcare composition and a film comprises a blend of a polyvinyl alcoholhomopolymer resin and an anionic polyvinyl alcohol copolymer resin, thenboth the first water soluble film and the second water soluble filmcomprise blends that include 65 wt. % or greater of an anionic polyvinylalcohol copolymer resin; and provided that when the composition is afabric care or household care composition and a film comprises a blendof at least two anionic polyvinyl alcohol copolymer resins, then boththe first water soluble film and the second water soluble film compriseblends of at least two anionic polyvinyl alcohol copolymer resins.